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By Arne F. Westgren

X-ray analysis and single-crystal study have been utilized in recent years as a new means of following constitutional changes in alloys. If such transformations can be suppressed by rapid cooling, they can be followed at room temperature in a particularly convenient manner. In the following we shall consider changes in solubility and polymorphic transformations with particular reference to phenomena of the age-hardening type. Finally a thermodynamic viewpoint is developed for examining such transformations. Changes in Solubility 1. Determinations of solubility limits in the solid state which show decreasing solubility with falling temperature are made as follows: A series of alloys extending into the heterogeneous region is prepared and quenched fromas high a temperature as possible, whereupon their lattice parameters are determined. Then one or more alloys are quenched from temperatures at which they are heterogeneous and their lattice parameters likwwise determined. For the purpose of determining the parameter the apparatus shown in Fig. 1 has been very useful for it produces sharp films in a short time which can be accurately read. High-order reflections (interferences) from the object are recorded on a film which is placed exactly perpendicular to the X-ray beam. The specimen usually has the shape of a small round bar.l Fig. 2 shows a selection of such exposures of silver-rich Cu-Ag alloys, and Fig. 3 gives the measurements made from these films. Fig. 4 gives the solubility curve which results.2 This curve is shifted to lower concentrations than the curve that is obtained from metallographic or physical methods. The X-ray method unquestionably gives more reliable data

Jan 1, 1931

By S. N. Kesten, Richard Murphy, A. H. Land, W. F. James

Introduction—by W. F. James and A. H. Lang This paper describes the geology and present state of development of uranium and thorium deposits in Canada. It is expected that this information will be added to that now being assembled from available American and British data to provide a background for engineers and others who may be called upon in the future to examine or search for radioactive deposits. Some generaliza- tions regarding the Canadian deposits are included, but many of these are necessarily tentative. The information contained in the paper is up to date for the end of 1948. The information contained in this paper has been derived from many sources. Much of it is from the records of the Canadian government-owned Eldorado Mining and Refining (1944) Limited and from examinations of government and private properties made by officers of the Geological Survey of Canada. Some information on privately-owned properties has been quoted from other sources mentioned in the text. The information has been assembled by W. F. James of Eldorado Mining and Refining (1944) Limited and A. H. Lang of the Geological Survey of Canada, who have written the sections for which they are credited. The description of the Eldorado mine is based on reports by Richard Murphy, formerly chief geologist for Eldorado; the report by Mr. Murphy was published previously by the Canadian Institute of Mining and Metallurgy,' to whom the writers are indebted for permission to repub-lish. The section dealing with the geology of and development work in the Goldfields area, where Eldorado has important holdings, is by S. N. Kesten, field geologist for Eldorado. The geological diagram of the Goldfields area (fig. 2) was kindly supplied by A. M. Christie of the Geological Survey of Can-

Jan 1, 1951

By W. F. James, Richard Murphy, S. N. Kesten, A. H. Land

Introduction—by W. F. James and A. H. Lang This paper describes the geology and present state of development of uranium and thorium deposits in Canada. It is expected that this information will be added to that now being assembled from available American and British data to provide a background for engineers and others who may be called upon in the future to examine or search for radioactive deposits. Some generaliza- tions regarding the Canadian deposits are included, but many of these are necessarily tentative. The information contained in the paper is up to date for the end of 1948. The information contained in this paper has been derived from many sources. Much of it is from the records of the Canadian government-owned Eldorado Mining and Refining (1944) Limited and from examinations of government and private properties made by officers of the Geological Survey of Canada. Some information on privately-owned properties has been quoted from other sources mentioned in the text. The information has been assembled by W. F. James of Eldorado Mining and Refining (1944) Limited and A. H. Lang of the Geological Survey of Canada, who have written the sections for which they are credited. The description of the Eldorado mine is based on reports by Richard Murphy, formerly chief geologist for Eldorado; the report by Mr. Murphy was published previously by the Canadian Institute of Mining and Metallurgy,' to whom the writers are indebted for permission to repub-lish. The section dealing with the geology of and development work in the Goldfields area, where Eldorado has important holdings, is by S. N. Kesten, field geologist for Eldorado. The geological diagram of the Goldfields area (fig. 2) was kindly supplied by A. M. Christie of the Geological Survey of Can-

Jan 1, 1951

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand or magnetite, in water, and, (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended sand or magnetite pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous; vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the introduction of feed and withdrawal of products, 'so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary is get the recoveries and grade of product desired. Sizes usually cleaned are plus ¼ in. or plus 1/8 -in. in the United States and plus 1/16-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about 1/8-in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media processes is progressing rapidly and it is likely that equipment, media, and procedures will be developed to clean sizes down to 0.5 mm. efficiently and at low cost.

Jan 1, 1950

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the south- eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States. Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). [ ] The fuller's earth type of clay is characterized by a lack of plasticity, relatively adsorbent, foliated structure, and does not swell to form a

Jan 1, 1939

By A. Satter

Studies of wellbore heat transtnission during the injection of a hot fluid, as either gas or liquid, have appeared in he literature. The present investigation takes into account the effect of condensation, which is of practical sig-nificance when considering steam injection operations. Calculation procedures are given for superheated and for saturated and undersaturated steam. Effects of injection rate, time, pressure, temperature and depth of a well on heat losses have been analyzed. The benefits of using a packer are discussed. Also presented are correlations for estimating heat losses involved during injection of saturated steam. INTRODUCTION Studies of wellbore heat losses during the injection of a hot fluid have appeared in the literature. Ramey' has presented a useful solution for calculating temperature of a heated gas as a function of depth and injection time. Ramey and others have also presented solutions for the hot liquid case.'. ' No method is available to take into account the effect of condensation, which is of practical significance when considering steam injection operations. This paper presents a method of estimating the quality of a condensing fluid as a function of depth and time. The approach is basically the same as that used by Ramey. The following injected fluids and conditions are considered in this study: 1. Injection of superheated steam A. Decrease in temperature until cooled to the saturated state B. Condensation until condensed completely into hot (saturated) water 2. Injection of saturated or undersaturated steam; condensation until condensed completely into hot (saturated) water. Although this investigation does not include cooling of water after steam is completely condensed, Ramey's solution for the hot liquid case can be used for this purpose. The effects of various process variables on heat losses During the injection of steam into a well are investigated. THEORY QUALITY OF CONDENSING STEAM Predicting the behavior of condensing steam flowing down the injection wellbore requires an estimate of the quality of steam, i.e., the mass fraction of vapor in the mixture. Let us divide the total depth of the injection well into several segments which might be, but do not have to be, of equal magnitude. Consider condensation within a given depth interval AZ, the bottom of which is located at a depth Z from the surface (Fig 1). The following equation, derived in the Appendix- relates the quality of steam at the bottom of an interval to that at the top of the interval:

Jan 1, 1966

By J. D. McBeth, G. M. Potter, Ramon Pizarro

Heap leaching is used by the Carlin Gold Mining Co., Carlin, Nev., to supplement conventional processing of gold ore by agitation-leaching and countercurrent decantation. Selected open-pit ore containing about 0.072 oz Au per ton is crushed to 3/4 inch, dumped by truck on an asphalt pad, and leached by sprinkling with dilute cyanide solution for 7 days. The heap is then drained and removed by front-end loader to tailings disposal. About 70 percent of the gold is dissolved. Leach solution from the heap joins the pregnant solution from countercurrent decantation for gold recovery by zinc precipitation. Four leach pads, each with a capacity of 1,400 tons of ore, are in use. About 10,000 tons of ore are heap leached monthly from about April through October. Heap leaching is recessed during freezing weather. Labor, equipment, and reagent requirements for heap leaching are presented.

Jan 1, 1974

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By W. E. Keck, W. C. Lowry, G. C. Eggleston

The potential iron ores of Michigan can be classified from the stand-point of the predominant impurities into siliceous, sulphurous and phos-pllorous ores. Research on the flotation of each of these classes of ore was carried out in the following manner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly pure state. There are two varieties of the mineral—specular hematite and massive hematite. The latter is the principal variety, but the former is an impor-tant' mineral of iron in some of the potential ores. Because of this condition, flotation research was performed with both varieties. This research consisted essentially of: (I) a survey of the literature on hematite flotation, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a proprietary frother and oleic acid or other soluble oils2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1939

By G. C. Eggleston, W. E. Keck, W. C. Lowry

The potential iron ores of Michigan can be classified from the stand-point of the predominant impurities into siliceous, sulphurous and phos-pllorous ores. Research on the flotation of each of these classes of ore was carried out in the following manner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly pure state. There are two varieties of the mineral—specular hematite and massive hematite. The latter is the principal variety, but the former is an impor-tant' mineral of iron in some of the potential ores. Because of this condition, flotation research was performed with both varieties. This research consisted essentially of: (I) a survey of the literature on hematite flotation, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a proprietary frother and oleic acid or other soluble oils2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1939

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.' These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,' one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z' alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

By W. M. Tuddenham, R. J. P. Lyon

In many areas surrounding the orebodies in mining districts rocks have been bleached and altered by the ore-forming solutions and have been oxidized during later weathering processes. A number of the rock-forming silic-ates have been broken down to clay, sericitic micas and chlorites have been developed, and pyrite may be found hundreds of feet outside the economic limits of the orebody. These halos of altered ground are prime targets used by geologists in many districts to delineate promising sites for drilling. Both in the field and in the laboratory it is often difficult to map these mineralogical changes in the halos in detail without numerous petrologic examinations. The secondary minerals are generally fine-grained, and since conversion of one mineral to another is often progressive, many alteration processes have not proceeded to completion (feldspars to clay to sericite mica). Qualitative detection of these minerals is difficult; quantitative determination is frequently impossible.

Jan 1, 1960

By Richard H. Rein, John Chipman

Liquid slags of the system SiO2-Ca0-MgO-A1~03 were equilibrated with liquid Fe-Si-C alloys in graphite or Sic crucibles at 1600°C in pure CO gas at atmospheric pressure, and the silicon content of both phases determined. Ternary slugs of the systern SiO2-CaO-A12O3 were also studied at 1550°C. The silicon content of the metal phase saturated with both graphite and SIC is 22.0pct at 1550°C and In the iron blast furnace, as in nearly all carbon-reduction processes, some silicon is transferred from slag to metal. The importance of this reaction is enhanced by its indirect effect on the transfer of sulfur from metal to slag, and this has stimulated a comprehensive research program on the equilibrium distribution of silicon between slag and metal. Earlier studies'-3 of this same problem provided data for calculation of the thermodynamic activities4 of the components in SiO,-CaO-A1,O3 slags. 22.4 pct at 1600°C. The temperature at which the phases cristobalite, gvaphite, $ SiC, liquid slag, Fe-Si-C alloy, and CO gas at 1 atm pressure can coexist in equilibrium was found to be 1533°C. The results agree well with earlier studies. They are shown graphically as lines of constant silicon cmtent in the metal which also are lines of constant SiO, activity in the slag.

Jan 1, 1963

By M. T. Melvin, N. P. Kripakov

The practical application of a post-processing modeling procedure to simulate progressive rock failure around the periphery of coal mine entries is presented. This numerical scheme utilizes a simple rock model that incorporates easily obtainable input parameters consistent with basic rock mechanics principles. These parameters include the cohesion, angle of internal friction, modulus of elasticity, and Poisson's ratio of the bedded deposits that comprise the imediate roof, coal seam, and immediate floor. The geometry of the entry, along with the in situ stresses existing at a mine site prior to mining, are also considered in the analysis. The potential of this procedure as a predictive tool in determining the extent of pillar rib fracturing and yielding of the immediate roof and floor is evaluated assuming a Mohr- Coulomb failure criterion. The procedure is designed to be user oriented and is adaptable to any finite element code with linear elastic capability, making it particularly attractive to users with limited budgets and computer size.

Jan 1, 1983

By John Mathews

IT is twenty years since the writer made his first molybdenum steels and others were making them commercially five years earlier but the prevailing opinion seems to be that molybdenum steels are new; from time to time the daily press speaks of important discoveries in Europe and intimates that American steel makers have much to learn in regard to alloy steels. The earlier experiments were largely confined to the use of relatively high percentages of molybdenum in tool steels and permanent magnet steels. Recent developments deal with the types of alloy structural steels used for airplane, automobile, and other engineering requirements; in these, the molybdenum content is usually less than 1 per cent. The earlier types generally have been unsuccessful commercially, but the newer types of steels are becoming of increasing importance. The war showed our dependence on foreign sources for alloying metals; molybdenum alone is widely distributed in the United States and seemingly abundant. Many deposits are not now of commercial interest, owing to location and relatively small amount of ore available, but other deposits are being developed and a stable source of supply seems well assured. In tool and magnet steels, it was early found that 1 part of molybdenum was equivalent to from 2 to 2.5 parts of tungsten. The permanent magnet steels investigated by Madame Curie,1 in 1898, contained from 3.36 to 4.05 per cent. molybdenum; in 1902, Dr. E. L. French and the writer thoroughly tested steels containing from 2:0 to 4.0 per cent. These steels gave satisfactory tests for permanence, but were low in residual density and much more sensitive to hardening than the corresponding tungsten products. We discontinued work with them, therefore, and have no advice that such steels have been used commercially here or abroad.

Jan 2, 1921

By E. V. Potter, E. T. Hayes, H. C. Lukens

Large volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that bite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.l.2 The close relationship between iron and manganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. Apparatus The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of IOO C.C. for a 60-cm. length. For larger changes in gas volumes, auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By I. R. Kramer

The stress associated with the surface layer was deter-minedfor iron and molybdcnum. These measurements show that the surface layer plays a very important role in the plastic deformation of bcc metals. From the relationship between strain arui the surface layer stress and the back stress imposed by the internal obstacles, it is Proposed that the term of of the Hall-Petch equation is related only THE large number of studies on plastic flow of bcc metals have failed to delineate clearly the nature of the obstacles influencing dislocation movement. Since there have been numerous articles which have reviewed the mechanisms proposed to explain various aspects of plastic flow of bcc metals (for example, conrad1 and Keh and weissmann2), no attempt will be made here to discuss their conclusions. However, it should be to the surface stress while the term Kfd is the stress required to move dislocations through internal obstacles. Further, it was possible to derive the well-known empirical equation C = , and it is shown that the terprz a is comprised of two terms: a term Cs associated with the surface layer stress and Ci related to internal dislocation obstacles. pointed out that in all of these publications it has been tacitly assumed that plastic flow occurred uniformly throughout the cross section of the specimen (except, of course, for the Luders band region), It has generally been further assumed that the nature and distribution of the obstacles opposing the motion of dislocations are of the same type throughout. The role of the surface layer in bcc metals has not, as yet, been considered even though its role in fcc metals has been shown clearly to be of primary importance.3-5 Investigations on fcc metals have shown that at the onset of plastic deformation a surface layer acts to

Jan 1, 1968

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By D. Harker, M. J. Murphy

The mechanism by which age-hardening takes .place is still not completely understood. The principal theories range from the extreme of "precipitaiion-hardening" to that of "order-hardening," with many intermediate gradations. In the hope of obtaining new data on which to base a choice among the many theories, the authors have made electron micrographs of formvar replicas taken from metallic specimens at various stages of age-hardening. The results so obtained on an alloy of 2 per cent beryllium in copper and one of 20 per cent molybdenum in iron will be described in the following pages, as well as the technique used in preparing the replicas. Preparation of Formvae. Replicas of Metallic Specimens This section is concerned with the techniques that have roved successful in preparing formvar replicas for studying the microstructure of metals with the electron microscope. Because of its simplicity and accuracy, the formvar replica1 method developed in the General Electric Research Laboratory has been used exclusively, since it is much simpler than the silica replica method of Heidenreich and Peck2 and produces as good results. The formvar method to be described requires a technique acquired only by practice, and no foolproof set of rules can be given. it is a rapid method and a replica can be obtained in less than five minutes under favorable conditions. This does not mean that perfect replicas can be produced every five minutes, but rather that one can well afford to take several strippings* in order to produce a replica of high quality. The metallographic technique required for replica work—very fine polishing and etching with very dilute solutions—is described here. It can be said, in general, that almost any surface that has been carefully prepared for a photomicrograph at 1000 or more diameters can be used to obtain a replica for the electron microscope. Preparation of Metallographic Specimens The preparation of the metallographic specimens is somewhat more exacting than that usually given to samples to be used for inspection under the light microscope. After much experimentation, it was concluded that the best method consists in polishing the metal through to the coarse cloth, then etching and repolishing on final cloth until the layer of distorted metal is removed. After this procedure has been completed, a dilute etch—to approximately the depth necessary for a micrograph at 1000 diameters—usually produces a sur-

Jan 1, 1945